EP1087657B1 - Wasserbasierte mirkoemulsion eines pyrethroids - Google Patents

Wasserbasierte mirkoemulsion eines pyrethroids Download PDF

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Publication number
EP1087657B1
EP1087657B1 EP99920406A EP99920406A EP1087657B1 EP 1087657 B1 EP1087657 B1 EP 1087657B1 EP 99920406 A EP99920406 A EP 99920406A EP 99920406 A EP99920406 A EP 99920406A EP 1087657 B1 EP1087657 B1 EP 1087657B1
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Prior art keywords
clear
microemulsion
concentrate
prepared
matrix
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EP99920406A
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English (en)
French (fr)
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EP1087657A4 (de
EP1087657A1 (de
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Kolazi S. Narayanan
Domingo Jon
Robert M. Ianniello
Donald Prettypaul
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ISP Investments LLC
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ISP Investments LLC
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Classifications

    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/02—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing liquids as carriers, diluents or solvents
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N53/00—Biocides, pest repellants or attractants, or plant growth regulators containing cyclopropane carboxylic acids or derivatives thereof

Definitions

  • This invention relates to a delivery system for agriculturally active chemicals, and, more particularly, to a clear, one-phase, efficacious aqueous microemulsion for delivering a pyrethroid insecticide at a high loading.
  • Agriculturally active chemicals are most preferably applied in the form of aqueous emulsions, solutions or suspensions. Occasionally, they may also be applied in the form of a dust wherein the active ingredient is adsorbed onto or mixed with a finely divided inert carrier material, such as, china clay, or the like. With such powdered or dust compositions, drift due to wind is a problem and consequently, liquid formulations are preferred.
  • U.S. Patent Number 5,317,042 disclosed a clear stable, efficacious aqueous microemulsion of a pyrethroid insecticide, alone, or in a complex mixture, obtained by mixing the insecticide with an inert matrix composition containing a defined mixture of nonionic surfactant to form a microemulsion concentrate, and diluting with water.
  • the inert matrix composition consisted of a predetermined mixture of nonionic surfactants which also included nonylphenol ethoxylate with HLB > 6. However, the presence of nonylphenol ethoxylate in the formulation may be considered detrimental in some cases.
  • US 5,389,688 describes a highly stable composition composed of a water insoluble agriculturally active ingredient, a surfactant, a lactam of defined formula and at least about 80% by weight of water.
  • the composition is in the form of a microemulsion.
  • the lactam may be either or both of methyl pyrrolidone and octyl pyrrolidone.
  • aqueous microemulsion a pyrethroid insecticide which is free of nonylphenol ethoxylate, and which is stable upon formation, and which can be used within a relatively long time, without significant hydrolysis or precipitation.
  • a pyrethroid is a class of well known and widely-used insecticides of which cypermethrin, o-allethrin, permethrin and tetramethrin are representative examples.
  • a clear, efficacious, aqueous, microemulsion of a pyrethroid was formulated having the following components, in parts by weight.
  • Component Suitable Preferred (a) Pyrethroid e.g. cypermethrin 0.0005-4 0.010-3 (b) C 1 -C 4 alkyl pyrrolidone e.g.
  • N-methyl pyrrolidone 0-6 0.015-4 C 6 -C 18 alkyl pyrrolidone, e.g. octyl pyrrolidone 0.0002-4 0.005-2
  • EO/PO block copolymer e.g. Pluronic ® L31 0-3 0.05-1.5
  • Ethoxylate of Castor Oil or tristyryl phenol ethoxylate e.g. Alkamuls ® EL-620 or Soprophor® BSU 0.003-10 0.04-6
  • Phosphate ester e.g. Soprophor ® 3D-33, Rhodafac ® RS 710 or Rhodafac ® RA 600 0-1% 0.005-0.6% (8) Water >80 90-99.99 100.0 100.0
  • This composition is a stable, one-phase, efficacious microemulsion of pH ⁇ 4 at ambient temperatures free of nonylphenol ethoxylate and which is designed for use after preparation.
  • compositions of the invention include: permethrin; permethrin + Kathon ® , D-allethrin; tetramethrin; deltamethrin; piperonyl butoxide; mixed pyrethroids; dicofol; tefluthrin; resmethrin; phenothrin; kadethrin; bifenthrin; cyhalothrin; cycloprothrin; tralomethrin; cyfluthrin; fenvalerate and isomers; fenpropathrin; fluvalenate; rotenone; biphenyl compounds like, methoxychlor; chlorbenzilate; bromopropylate and chlorfenethol.
  • compositions of the invention could be stored at ⁇ -5°C. without freezing or separating the active.
  • An Inert Matrix Composition for forming a stable, clear efficacious Microemulsion Concentrate (MEC). Upon dilution of the concentrate with water, an aqueous microemulsion is provided.
  • the Inert Matrix Composition was prepared by mixing predetermined amount of C 8 alkylpyrrolidone, defined nonionic surfactants, and preferably with C 1 alkylpyrrolidone.
  • the Agricultural Active Chemical (AAC) was added and the mixture shaken until the dissolution of AAC or the mixture became homogeneous. Normally this took about thirty minutes to two hours.
  • a MEC was obtained which was either diluted immediately at ratios 1:10, 1:100, 1:1000 and 1:10,000 or stored.
  • the water based microemulsion were prepared by adding the required quantity of the concentrate to water.
  • the dilution water was either deionized water or World Health Organization (WHO) standard hard water of hardness of 1000 ppm expressed as CaCO 3 equivalent.
  • WHO World Health Organization
  • aqueous microemulsion composition of the invention made according to the above procedure are summarized from TABLE 1 to TABLE 4 below, wherein the components are in grams. The stability of the microemulsion after standing at room temperature for a considerable period are also included.
  • a series of microemulsion and miniemulsion concentrates were prepared using various amounts of cypermethrin.
  • An inert matrix M1 was prepared first by mixing 21.3 g of N-methylpyrrolidone, 9.3 g N-octylpyrrolidone, 9.3 g of Pluronic L31, 56.0 g of Soprophor BSU and 4.0 g of Soprophor 3D-33.
  • Microemulsion concentrates were prepared by mixing 10 g, 15 g, 20 g and 25g cypermethrin with 90 g, 85 g, 80 g, and 75 g of matrix M1, respectively, as seen in Table 3.
  • microemulsion concentrate were diluted at ratios 1:10, 1:100 and 1:1000 with 1000 ppm hard water. All the diluted samples were clear except at 1:10 and 1:100 aqueous dilutions of 20% and 25% cypermethrin. At these dilutions, miniemulsions were obtained that were stable for at least a day. The particle size at 1:10 dilution of 10% and 15% cypermethrin were less than 0.013 and 0.014 microns at 90% population, respectively. Freeze/thaw stability studies between 5 and -10°C were carried out with the concentrate containing 15% cypermethrin. The results showed a stable, liquid formulation at the lowest temperature described.
  • N-methylpyrrolidone in the microemulsion of Example 1 was investigated.
  • An inert matrix M2 was prepared first by mixing 10 g N-octylpyrrolidone, 10 g of Pluronic L31, 60 g of Soprophor BSU and 4.3 g of Soprophor 3D-33.
  • a concentrate was prepared by mixing 15 g of cypermethrin with 85 g of the matrix M2.
  • the microemulsion concentrate was diluted at ratios 1:10, 1:100 and 1:1000 with 1000 ppm hard water. All the diluted samples were clear. Freeze/thaw stability study between 5 and -10°C carried out with the concentrate showed a stable, thick paste at -5°C and lower temperatures.
  • N-octylpyrrolidone The role of N-octylpyrrolidone in the microemulsion of Example 1 was investigated.
  • An inert matrix M3 was prepared first by mixing 20 g N-methyl-pyrrolidone, 8.7 g of Pluronic L31, 52.8 g of Soprophor BSU and 3.7 g of Soprophor 3D-33.
  • a concentrate was prepared by mixing 15 g of cypermethrin with 85 g of matrix M3.
  • the microemulsion concentrate was diluted at ratios 1:10, 1:100 and 1:1000 with 1000 ppm hard water. All the diluted samples were stable and clear except at 1:100 dilution, where a precipitate was formed. Freeze/thaw stability study between 5 and -10°C carried out with the concentrate showed a stable, thick paste at -5°C and lower temperatures.
  • Example 1 Similarly, the role of both N-methylpyrrolidone and N-octylpyrrolidone in the microemulsion of Example 1 was investigated.
  • An inert matrix M4 was prepared first by 11.4 g of Pluronic L31, 68.7 g of Soprophor BSU and 4.9 g of Soprophor 3D-33.
  • a concentrate was prepared by mixing 15 g of cypermethrin with 85 g of matrix M4. The microemulsion concentrate was diluted at ratios 1:10, 1:100 and 1:1000 with 1000 ppm hard water. All the diluted samples were stable and clear except at 1:10 dilution, where a precipitate was formed.
  • Example 1 The experiment of Example 1 was repeated after replacing Soprophor BSU in Matrix M1 with equal weight of Alkamuls EL 620 (Matrix M5).
  • Microemulsion concentrates were prepared by mixing 10 g, 15 g, 20 g and 25 g cypermethrin with 90 g, 85 g, 80 g, and 75 g of matrix M5, respectively, as seen in Table 4.
  • the above microemulsion concentrate were diluted at ratios 1:10, 1:100 and 1:1000 with 1000 ppm hard water. All the diluted sample formed clear microemulsions except those samples diluted at 1:10 aqueous dilution with 15%, 20% and 25% cypermethrin.
  • hazy miniemulsions were obtained that were stable for at least a day at room temperature.
  • the solution was a clear microemulsion and the particle size was less than 0.04 microns at 90% population.
  • Freeze/thaw stability study between 5 and -10°C carried out with the microemulsion concentrate containing 15% cypermethrin showed a stable, liquid formulation at the lowest temperature described.
  • HPLC analysis of the concentrate containing 15% cypermethrin showed greater than 90% retention of a.i. after storing the sample at 52°C for 18 days.
  • N-methylpyrrolidone was investigated.
  • An inert Matrix M6 was prepared first by mixing 10 g N-octylpyrrolidone, 10 g of Pluronic L31, 60.6 g of Alkamuls EL 620 and 4.3 g of Soprophor 3D-33.
  • a concentrate was prepared by mixing 15 g of cypermethrin with 85 g of Matrix M6.
  • the microemulsion concentrate was diluted at ratios 1:10, 1:100 and 1:1000 with 1000 ppm hard water. All the diluted samples were stable and clear except at 1:100 dilution, where a precipitate was formed. Freeze/thaw stability study between 5 and -10°C carried out with the microemulsion concentrate showed the sample frozen at -5°C and lower temperature.
  • N-octylpyrrolidone was investigated.
  • An inert Matrix M7 was prepared first by mixing 20 g N-methylpyrrolidone, 8.7 g of Pluronic L31, 52.6 g of Alkamuls EL 620 and 3.7 g of Soprophor 3D-33.
  • a microemulsion concentrate was prepared by mixing 15 g of cypermethrin with 85 g of Matrix M7. The microemulsion concentrate was diluted at ratio 1:10, 1:100 and 1:1000 with 1000 ppm hard water. All the diluted samples were stable and clear except at 1:100 dilution, where a precipitate was formed. Freeze/thaw stability study between 5 and -10°C carried out with the emulsifiable concentrate showed a stable, liquid formulation at the lowest temperature described.
  • Example 6 the role of both N-methylpyrrolidone and N-octylpyrrolidone in the microemulsion of Example 6 was investigated.
  • An inert matrix M8 was prepared first by 11.4 g of Pluronic L31, 68.7 g of Alkamuls EL 620 and 4.9 g of Soprophor 3D-33.
  • a concentrate was prepared by mixing 15 g of cypermethrin with 85 g of matrix M8.
  • the microemulsion concentrate was diluted at ratio 1:10, 1:100 and 1:1000 with 1000 ppm hard water. Precipitate was found in all the diluted samples, except at 1:1000 dilution, where it remained clear.
  • Example 5 to Example 8 Freeze/thaw stability study between 5 and -10°C carried out with the microemulsion concentrate showed the sample frozen at 0°C and lower temperature. Therefore, the results of Example 5 to Example 8 indicate both N-methylpyrrolidone and N-octylpyrrolidone are required to obtain a stable, clear solution with all of the aqueous dilutions in Example 5, and N-methylpyrrolidone is needed to prevent freezing of the samples at temperature below -5°C.
  • An inert matrix M9 was prepared first by mixing 19.5 g of N-methylpyrrolidone, 8.6 g N-octylpyrrolidone, 8.6 g of Pluronic L31, 52.8 g of Alkamuls EL 620 and 0.5 g of Rhodafac RA 600.
  • a microemulsion concentrate was prepared by mixing 10 g of cypermethrin with 90 g of matrix M9. The above microemulsion concentrate was diluted at ratio 1:10, 1:100 and 1:1000 with 1000 ppm hard water. The samples diluted at ratio 1:10 and 1:1000 were found clear. The sample diluted at 1:100 ratio was found to precipitate in the form of gel within a day. When distilled water was used in place of 1000 ppm hard water, no gel was found at 1:100 dilution ratio.
  • An inert matrix M10 was prepared first by mixing 18.6 g of N-methylpyrrolidone, 8.1 g N-octylpyrrolidone, 8.1 g of Pluronic L31, and 50.2 g of Alkamuls EL 620.
  • a microemulsion concentrate was prepared by mixing 15 g of cypermethrin with 85 g of matrix M10. The above concentrate was diluted at ratio 1:10, 1:100 and 1:1000 with 1000 ppm hard water. All diluted, aqueous samples were found clear.
  • An inert matrix M11 was prepared first by mixing 19.7 g of N-methylpyrrolidone, 8.6 g N-octylpyrrolidone, 8.6 g of Pluronic L31, 51.8 g of Alkamuls EL 620 and 1.4 g of Rhodafac RS 710.
  • a microemulsion concentrate was prepared by mixing 10 g of cypermethrin with 90 g of matrix M11. The above concentrate was diluted at ratios 1:10, 1:100 and 1:1000 with 1000 ppm hard water. All diluted, aqueous samples were found clear.
  • HPLC analysis of the microemulsion concentrate showed greater than 95% retention of a.i. after storing the sample at 52°C for 18 days.
  • An inert matrix M12 was prepared first by mixing 17.5 g of N-methylpyrrolidone, 7.6 g N-octylpyrrolidone, 7.6 g of Pluronic L31, 46 g of Alkamuls EL 620 and 1.2 g of Rhodafac RS 710.
  • a microemulsion concentrate was prepared by mixing 20 g of cypermethrin with 80 g of matrix M12. The above concentrate was diluted at ratio 1:10, 1:20, 1:100 and 1:1000 with 1000 ppm hard water. All diluted aqueous samples were found clear. The particle size at 1:10 and 1:20 dilutions were less than 0.02 and 0.05 microns, at 90% population, respectively.
  • HPLC analysis of the concentrate showed greater than 95% retention of the a.i. after storing the sample at 52°C for 18 days.
  • An inert matrix M13 was prepared first by mixing 17 g of N-methylpyrrolidone, 7.4 g N-octylpyrrolidone, 7.4 g of Pluronic L31, 22.4 g of Soprophor BSU, 22.5 g of Alkamuls EL 620 and 3.2 g of Soprophor 3D33.
  • a microemulsion concentrate was prepared by mixing 20 g of cypermethrin with 80 g of matrix M13. The concentrate remained stable and single phase after storage in an oven for 13 days at 52°C. The above concentrate was diluted at ratio 1:10, 1:100 and 1:1000 with 1000 ppm hard water. All diluted, aqueous samples were found clear.
  • Table 5 shows the microemulsion concentrate for several pyrethroids.
  • An inert matrix M14 was prepared first by mixing 21.9 g of N-methylpyrrolidone, 9.6 g N-octylpyrrolidone, 9.6 g of Pluronic L31, and 59 g of Alkamuls EL 620.
  • Several microemulsion concentrates were prepared by mixing 10 g of either D-allethrin, permethrin, piperonyl butoxide, or bioresmethrin, with 90 g of matrix M14.
  • Microemulsion concentrates were also prepared with 10 g and 5 g of deltamethrin with 90 g and 95 g of matrix M14, respectively.
  • Microemulsion concentrates were prepared with 15 g and 5 g of penconazole with 85 g and 95 g of matrix M14, respectively.
  • a microemulsion concentrate was also prepared with 24 g of mixture of D-allethrin/piperonyl butoxide at 4/20 ratio with 76 g of matrix M14.
  • the stability results, at room temperature, of the above microemulsion concentrates after dilution at 1:10, 1:100 and 1:1000 with 1000 ppm hard water are as follows, D-allethrin, permethrin, piperonyl butoxide, and bioresmethrin remained stable and clear upon dilution for 14 days.
  • An inert Matrix M15 was prepared first by mixing 22 g of N-methylpyrrolidone, 10 g N-octylpyrrolidone, 10 g of Pluronic L31, and 58 g of Alkamuls EL 620. Matrix M15 was added to a premixed agricultural active chemicals (PAA) consisting of 0.05 g allethrin, 0.15 g permethrin, 0.2 g tetramethrin and 1.0 g piperonyl butoxide. The mixture of matrix M15 and PAA were shaken until the agricultural actives dissolved in the inert matrix M15 or the mixture became homogeneous. Normally this took about thirty minutes to two hours.
  • PAA premixed agricultural active chemicals
  • the concentrate obtained was then diluted to 100 grams by adding 1000 ppm hard water following the World Health Organization (WHO) standard and expressed as CaCO 3 equivalent.
  • WHO World Health Organization
  • a clear, microemulsion system was found by increasing the amount of the Matrix M15 in the concentrate while maintaining the amount of actives constant, and diluting the concentrate with hard water up to 100 g.
  • the optimal concentration of Matrix M15 in the microemulsion system was found to be 4.01 g in the concentrate.
  • the concentrate and diluted samples were visually examined for clarity, precipitation, and separation or turbidity at ambient temperatures. Stable formulations were observed for 2 weeks.
  • the aqueous microemulsion compositions of the invention made according to the above procedure are summarized from Table 6, wherein the components are in grams.
  • a series of microemulsion and miniemulsion concentrates were prepared using various amounts of permethrin.
  • An inert matrix M16 was prepared first by mixing 22.2 g of N-methylpyrrolidone, 9.7 g N-octylpyrrolidone, 9.7 g of Pluronic L31, and 58.4 g of Alkamuls EL 620.
  • Emulsifiable concentrates were prepared by mixing 30 g, 40 g, 50 g permethrin with 70 g, and 60 g, and 50 g of matrix M16, respectively, as seen in Table 7.
  • the above emulsifiable concentrate were diluted at ratios 1:10, and 1:100 with 1000 ppm hard water. The results of the stability after dilution are shown in Table 7. Further dilutions of the emulsifable concentrates to 1%, 1.5% and 2% permethrin were also undertaken. The stability results are shown in Table 8.
  • An emulsifiable concentrates with permethrin as the active ingredient was prepared by mixing 40 g of permethrin with 60 g of Igepal CO-630. The concentrate remained stable and single phase on storage.
  • the above emulsifiable concentrate were diluted at ratio 1:10, 1:20, 1:27, 1:40, and 1:100 (5%, 2%, 1.5%, 1% and 0.4% a.i. respectively) with 1000 ppm hard water. All diluted, aqueous samples were found to form two phases within one-half hour after mixing.

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  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Dentistry (AREA)
  • Plant Pathology (AREA)
  • Engineering & Computer Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Agronomy & Crop Science (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Toxicology (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
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Claims (3)

  1. Klare, einphasige, wirksame wässrige Mikroemulsionszusammensetzung aus einem Pyrethroid-Insektizid, das frei von Nonylphenolethoxylat ist und Folgendes umfasst:
    (a) 0,01-3 Gew.-% des Pyrethroids;
    (b) 0,015-4 Gew.-% eines N-C1-C4-Alkylpyrrolidons;
    (c) 0,005-2 Gew.-% eines C6-C18-Alkylpyrrolidons;
    (d) 0,05-1,5 Gew.-% eines EO/PO-Blockcopolymer-Tensids;
    (e) 0,04-6 Gew.-% eines ethoxylierten Rizinusöls oder eines Tristyrylphenolethoxylats;
    (f) 0,0005-0,6 Gew.-% eines Phosphatesters als pH-Puffer und
    (g) 90-99,99 Gew.-% Wasser.
  2. Mikroemulsionszusammensetzung nach Anspruch 1, worin (a) Cypermethrin ist, (b) N-Methylpyrrolidon ist, (c) N-Octylpyrrolidon ist und (e) ein ethoxyliertes Rizinusöl ist.
  3. Mikroemulsionszusammensetzung nach Anspruch 1, worin (a) Permethrin, Deltamethrin, D-Allethrin, Bioresmethrin, Penconazol, ein Gemisch von D-Allethrin/Piperonylbutoxid oder ein Gemisch von D-Allethrin/Permethrin/Tetramethrin/Piperonylbutoxid ist.
EP99920406A 1998-06-17 1999-05-07 Wasserbasierte mirkoemulsion eines pyrethroids Expired - Lifetime EP1087657B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US98658 1998-06-17
US09/098,658 US6045816A (en) 1998-06-17 1998-06-17 Water-based microemulsion of a pyrethroid
PCT/US1999/010121 WO1999065300A1 (en) 1998-06-17 1999-05-07 Water-based microemulsion of a pyrethroid

Publications (3)

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EP1087657A1 EP1087657A1 (de) 2001-04-04
EP1087657A4 EP1087657A4 (de) 2005-01-12
EP1087657B1 true EP1087657B1 (de) 2008-07-02

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US (2) US6045816A (de)
EP (1) EP1087657B1 (de)
JP (1) JP2002518295A (de)
KR (1) KR100758226B1 (de)
AT (1) ATE399463T1 (de)
AU (1) AU3790999A (de)
BR (1) BR9911319B1 (de)
DE (1) DE69939018D1 (de)
WO (1) WO1999065300A1 (de)

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JP2002518295A (ja) 2002-06-25
ATE399463T1 (de) 2008-07-15
AU3790999A (en) 2000-01-05
EP1087657A4 (de) 2005-01-12
US6045816A (en) 2000-04-04
WO1999065300A1 (en) 1999-12-23
EP1087657A1 (de) 2001-04-04
BR9911319A (pt) 2006-02-14
DE69939018D1 (de) 2008-08-14
BR9911319B1 (pt) 2013-06-11
KR100758226B1 (ko) 2007-09-12
KR20010052914A (ko) 2001-06-25
US6251416B1 (en) 2001-06-26

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